稀土摻雜硅酸鹽電子俘獲型材料及其發(fā)光性能的研究
發(fā)布時間：2018-07-26 19:36
【摘要】：電子俘獲型材料(Electron trapping materials)具有存儲的特性,并且材料被長波波長的光激勵時,可以輻射出短波波長的光,因此它在光學領域的另外一個名稱為光激勵發(fā)光材料。光激勵發(fā)光材料因其獨特的性質,其在紅外探測、紅外光轉換、光存儲及X射線成像等諸多方面有其廣泛的應用前景。目前,可以商業(yè)化光激勵材料主要是堿土金屬硫化物系列,這種材料的光激勵發(fā)光初始激發(fā)亮度強度高,并且光存儲量大等諸多優(yōu)點。但是,硫化物的本身的致命缺陷就是熱穩(wěn)定差。同時,我們知道硫化物的分解,將會產生有毒害的物質,可以對自然環(huán)境造成嚴重的污染。因此,尋找一種化學性質穩(wěn)定,并且對環(huán)境污染少的光激勵材料已經成為當前的光激勵材料研究的重點。從所周知,硅酸鹽體系具有較好的化學穩(wěn)定性,并且耐高溫、抗腐蝕等優(yōu)點,是目前被廣泛的用作稀土發(fā)光材料的基質材料。其中,基質材料RSrSiO4:Eu2+(R=Sr/Li2)是一類傳統(tǒng)的LED (light emitting diodes)用的熒光粉,本論文以RSrSiO4:Eu2+(R=Sr/Li2)為研究對象,通過摻入另一種共激活劑的方式引入陷阱以提高其光激勵發(fā)光性能。主要的研究成果如下：1)在基質材料β-SrSiO4:Eu2+中,通過La3+離子摻雜有效的提高了樣品長余輝發(fā)光性能與光激勵發(fā)光性能。樣品的長余輝時間從幾分鐘增長到五十多分鐘,同時其光激勵初始強度、光激勵光存儲量等性能都有不同程度的提高。其原因是由于摻雜La3+離子的樣品本征存在的氧空位更加穩(wěn)定,因此其俘獲電子的能力得到很大的提高,這些增加的陷阱可以很大程度的提高材料的光激勵發(fā)光性能。2)在Li2SrSi04:Eu2+材料中,我們通過摻入四種不同的稀土離子(La3+/Nd3+/Dy3+ /Tm3+),研究發(fā)現(xiàn)不同的稀土離子對基質材料內部的微觀結構影響不同,通過比較發(fā)現(xiàn)La3+離子能有效的增強材料的不同溫度范圍的熱釋光強度,因此其對樣品的光激勵發(fā)光性能是有較大貢獻。同時發(fā)現(xiàn)Nd3+/Dy3+離子對樣品材料的長余輝發(fā)光性能是有貢獻的,而對光激發(fā)光性能影響較小,因而可以忽略,其中Dy3+離子對樣品的長余輝發(fā)光性能影響最大。而Tm3+離子可以有效的提高深陷阱區(qū)的熱釋光峰,不過在我們用近紅外光激勵時,不能使陷阱中的電子釋放出來,因而Tm3+離子對光激勵發(fā)光幾乎沒有貢獻。3)系統(tǒng)的研究了不同濃度La3+離子摻雜下Li2Sr0.997SiO4: 0.003Eu2+光激勵發(fā)光性能的變化。通過比較樣品的光致發(fā)光和光激勵發(fā)光光譜,說明樣品的發(fā)光都來自同一個發(fā)光中心,即Eu2+離子4f65d1→4f7的躍遷。經研究我們發(fā)現(xiàn),隨著La3+離子濃度增加樣品的光激勵發(fā)光性能逐漸提升,當La3+的摻雜濃度為0.008時,基質材料的光激勵發(fā)光初始強度和光激勵光存儲量性能均達到了最優(yōu)。同時研究了Dy3+離子對材料Li2Sr0.997SiO4:0.003Eu2+的熒光發(fā)光、長余輝發(fā)光性能的影響。通過實驗發(fā)現(xiàn),Dy3+離子的引入在一定程度上使得材料的熒光發(fā)光強度有所降低,這是因為Dyr3+的引入使得材料本征存在的氧空位更加穩(wěn)定,增強了其俘獲載流子的能力,因此,在光致發(fā)光過程中,這些陷阱將會俘獲部分載流子造成基質材料發(fā)光強度的降低。同時我們發(fā)現(xiàn)材料的長余輝性能隨著Dy3+離子的引入有所增強。
[Abstract]:Electron trapping materials has the characteristics of storage, and when the material is stimulated by long wave wavelengths, it can radiate the light of the short wave wavelength. Therefore, the other name in the optical field is the light excited luminescent material. The light excitation luminescent material is detected in infrared and infrared light conversion because of its unique properties. There are extensive applications in optical storage and X ray imaging. At present, commercialized light excitation materials are mainly alkaline earth metal sulfide series. The light excitation luminescence intensity of this material is high, and the amount of light storage is large. However, the fatal defect of the sulphide itself is the thermal stability. It is known that the decomposition of sulfides will produce toxic substances and can cause serious pollution to the natural environment. Therefore, looking for a light excitation material with stable chemical properties and less pollution to the environment has become the focus of current research on light excitation materials. It is well known that the silicate system has good chemical stability. With the advantages of high temperature resistance and corrosion resistance, it is widely used as a matrix material for rare earth luminescent materials. The matrix material RSrSiO4:Eu2+ (R=Sr/Li2) is a kind of traditional LED (light emitting diodes) phosphor. This paper is based on RSrSiO4:Eu2+ (R=Sr/Li2) as the research object and introduced by adding another Co activator. The main research results are as follows: 1) in the matrix material beta -SrSiO4:Eu2+, the long afterglow and light excitation properties of the sample are improved effectively by doping La3+ ions. The long afterglow time of the sample increases from a few minutes to more than 50 minutes, and the light excitation intensity and light excitation are also stimulated. The performance of the stored reserves has been improved in varying degrees. The reason is that the oxygen vacancies in the samples of the doped La3+ ions are more stable, so the ability to capture electrons is greatly improved. These increased traps can greatly improve the light excitation performance of the material.2) in the Li2SrSi04:Eu2+ material. Over the addition of four different rare earth ions (La3+/Nd3+/Dy3+ /Tm3+), it is found that different rare earth ions have different effects on the microstructure of the matrix materials. By comparison, it is found that La3+ ions can effectively enhance the thermoluminescence intensity of the materials at different temperature ranges, so it has a great contribution to the photoluminescence properties of the samples. It is found that the Nd3+/Dy3+ ions contribute to the long afterglow luminescence properties of the sample materials, but have little effect on the luminescence properties, and can be ignored, in which the Dy3+ ions have the greatest influence on the long afterglow luminescence properties of the samples, and the Tm3+ ions can effectively improve the thermal Shi Guangfeng in the deep trap region, but when we are excited by near infrared light, The electrons in the trap can not be released, so the Tm3+ ions have little contribution to the light excited luminescence. The system has studied the changes in the luminescence properties of the Li2Sr0.997SiO4: 0.003Eu2+ light stimulated by different concentrations of La3+ ions. By comparing the photoluminescence of the samples and the light excitation luminescence spectra, the luminescence of the samples comes from the same one. The luminescence center, that is, the transition of the Eu2+ ion 4f65d1 to 4F7. We have found that the luminescent properties of the samples increase gradually with the increase of the concentration of La3+ ions. When the doping concentration of La3+ is 0.008, the initial light excitation intensity and the optical storage performance of the matrix material have reached the best performance. At the same time, the Dy3+ ion pair is studied. The effect of fluorescent luminescence of Li2Sr0.997SiO4:0.003Eu2+ on the properties of long afterglow luminescence. It is found through experiments that the introduction of Dy3+ ions reduces the fluorescence intensity of the material to some extent. This is because the introduction of Dyr3+ makes the oxygen vacancies in the material more stable and the ability to capture the carrier. Therefore, the ability of the carrier to capture the carrier is enhanced. In the photoluminescence process, these traps will capture part of the carrier to reduce the luminescence intensity of the matrix material. We also find that the long afterglow properties of the material are enhanced with the introduction of Dy3+ ions.
【學位授予單位】：昆明理工大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：TB34;TQ422
本文編號：2147075
[Abstract]:Electron trapping materials has the characteristics of storage, and when the material is stimulated by long wave wavelengths, it can radiate the light of the short wave wavelength. Therefore, the other name in the optical field is the light excited luminescent material. The light excitation luminescent material is detected in infrared and infrared light conversion because of its unique properties. There are extensive applications in optical storage and X ray imaging. At present, commercialized light excitation materials are mainly alkaline earth metal sulfide series. The light excitation luminescence intensity of this material is high, and the amount of light storage is large. However, the fatal defect of the sulphide itself is the thermal stability. It is known that the decomposition of sulfides will produce toxic substances and can cause serious pollution to the natural environment. Therefore, looking for a light excitation material with stable chemical properties and less pollution to the environment has become the focus of current research on light excitation materials. It is well known that the silicate system has good chemical stability. With the advantages of high temperature resistance and corrosion resistance, it is widely used as a matrix material for rare earth luminescent materials. The matrix material RSrSiO4:Eu2+ (R=Sr/Li2) is a kind of traditional LED (light emitting diodes) phosphor. This paper is based on RSrSiO4:Eu2+ (R=Sr/Li2) as the research object and introduced by adding another Co activator. The main research results are as follows: 1) in the matrix material beta -SrSiO4:Eu2+, the long afterglow and light excitation properties of the sample are improved effectively by doping La3+ ions. The long afterglow time of the sample increases from a few minutes to more than 50 minutes, and the light excitation intensity and light excitation are also stimulated. The performance of the stored reserves has been improved in varying degrees. The reason is that the oxygen vacancies in the samples of the doped La3+ ions are more stable, so the ability to capture electrons is greatly improved. These increased traps can greatly improve the light excitation performance of the material.2) in the Li2SrSi04:Eu2+ material. Over the addition of four different rare earth ions (La3+/Nd3+/Dy3+ /Tm3+), it is found that different rare earth ions have different effects on the microstructure of the matrix materials. By comparison, it is found that La3+ ions can effectively enhance the thermoluminescence intensity of the materials at different temperature ranges, so it has a great contribution to the photoluminescence properties of the samples. It is found that the Nd3+/Dy3+ ions contribute to the long afterglow luminescence properties of the sample materials, but have little effect on the luminescence properties, and can be ignored, in which the Dy3+ ions have the greatest influence on the long afterglow luminescence properties of the samples, and the Tm3+ ions can effectively improve the thermal Shi Guangfeng in the deep trap region, but when we are excited by near infrared light, The electrons in the trap can not be released, so the Tm3+ ions have little contribution to the light excited luminescence. The system has studied the changes in the luminescence properties of the Li2Sr0.997SiO4: 0.003Eu2+ light stimulated by different concentrations of La3+ ions. By comparing the photoluminescence of the samples and the light excitation luminescence spectra, the luminescence of the samples comes from the same one. The luminescence center, that is, the transition of the Eu2+ ion 4f65d1 to 4F7. We have found that the luminescent properties of the samples increase gradually with the increase of the concentration of La3+ ions. When the doping concentration of La3+ is 0.008, the initial light excitation intensity and the optical storage performance of the matrix material have reached the best performance. At the same time, the Dy3+ ion pair is studied. The effect of fluorescent luminescence of Li2Sr0.997SiO4:0.003Eu2+ on the properties of long afterglow luminescence. It is found through experiments that the introduction of Dy3+ ions reduces the fluorescence intensity of the material to some extent. This is because the introduction of Dyr3+ makes the oxygen vacancies in the material more stable and the ability to capture the carrier. Therefore, the ability of the carrier to capture the carrier is enhanced. In the photoluminescence process, these traps will capture part of the carrier to reduce the luminescence intensity of the matrix material. We also find that the long afterglow properties of the material are enhanced with the introduction of Dy3+ ions.
【學位授予單位】：昆明理工大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：TB34;TQ422
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